Dual Effects of Cyclopentadienyl Ligands on Rh(III)-Catalyzed Dehydrogenative Arylation of Electron-Rich Alkenes

Despite extensive research on transition metal-catalyzed Fujiwara–Moritani type C–H olefinations, the alkenes used in these transformations are still mainly limited to active acrylate esters and styrenes. Selective aryl C–H olefination with electron-rich alkenes is recognized as a challenging issue. We herein report that simple and readily accessible electron-deficient [CpRh­(III)] and [Cp^CF₃Rh­(III)] (Cp^CF₃ = C₅Me₄CF₃) complexes are powerful catalysts for dehydrogenative arylation of electron-rich alkenes, including vinyl acetates, enamides, and vinyl ethers. Employing an electron-withdrawing Cp or Cp^CF₃ ligand instead of the privileged Cp* (C₅Me₅) ligand not only can facilitate the electrophilic aryl C–H rhodation but also can lower the olefin insertion barrier. Both electron-withdrawing and electron-donating directing groups such as -CONR₂ and -NHAc could be employed in these reactions, which provides convenient routes toward a series styryl acetates, N-acetylindoles, and aryl methyl ketones.